CN117757259A - Flame-retardant coupling agent synergistic glass fiber reinforced halogen-free flame-retardant polyamide composite material and preparation method thereof - Google Patents
Flame-retardant coupling agent synergistic glass fiber reinforced halogen-free flame-retardant polyamide composite material and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 118
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000004952 Polyamide Substances 0.000 title claims abstract description 46
- 229920002647 polyamide Polymers 0.000 title claims abstract description 46
- 239000003365 glass fiber Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 28
- 239000007822 coupling agent Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 43
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 23
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000004014 plasticizer Substances 0.000 claims abstract description 13
- 239000004970 Chain extender Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000005469 granulation Methods 0.000 claims abstract description 3
- 230000003179 granulation Effects 0.000 claims abstract description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 15
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 15
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- -1 dipropyl aluminum phosphinate Chemical compound 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- OHPZPBNDOVQJMH-UHFFFAOYSA-N n-ethyl-4-methylbenzenesulfonamide Chemical compound CCNS(=O)(=O)C1=CC=C(C)C=C1 OHPZPBNDOVQJMH-UHFFFAOYSA-N 0.000 claims description 3
- CMEUTESMNAONPQ-UHFFFAOYSA-N 4-azaniumyl-3-(4-methoxyphenyl)butanoate Chemical compound COC1=CC=C(C(CN)CC(O)=O)C=C1 CMEUTESMNAONPQ-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical compound [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 claims description 2
- CLZDQXZMNMNRAQ-UHFFFAOYSA-M [PH2]([O-])=O.C[Al+]C1=CC=CC=C1 Chemical compound [PH2]([O-])=O.C[Al+]C1=CC=CC=C1 CLZDQXZMNMNRAQ-UHFFFAOYSA-M 0.000 claims description 2
- JMJWMGLCPXGAFU-UHFFFAOYSA-M [PH2]([O-])=O.C[Al+]CC Chemical compound [PH2]([O-])=O.C[Al+]CC JMJWMGLCPXGAFU-UHFFFAOYSA-M 0.000 claims description 2
- ZJKCITHLCNCAHA-UHFFFAOYSA-K aluminum dioxidophosphanium Chemical compound [Al+3].[O-][PH2]=O.[O-][PH2]=O.[O-][PH2]=O ZJKCITHLCNCAHA-UHFFFAOYSA-K 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- NATWUQFQFMZVMT-UHFFFAOYSA-N n-ethyl-2-methylbenzenesulfonamide Chemical compound CCNS(=O)(=O)C1=CC=CC=C1C NATWUQFQFMZVMT-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 229940124530 sulfonamide Drugs 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- YPNZYYWORCABPU-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CC(=C)C(=O)OCC1CO1 YPNZYYWORCABPU-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 241000217776 Holocentridae Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 244000178289 Verbascum thapsus Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- QYHKLBKLFBZGAI-UHFFFAOYSA-N boron magnesium Chemical compound [B].[Mg] QYHKLBKLFBZGAI-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 239000006028 limestone Substances 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- 238000009941 weaving Methods 0.000 description 1
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Abstract
A flame-retardant coupling agent synergistic glass fiber reinforced halogen-free flame-retardant polyamide composite material and a preparation method thereof, wherein the raw materials comprise: 30-50 parts of polyamide resin; 0.3-4 parts of flame-retardant silane coupling agent; 20-60 parts of glass fiber; 10-18 parts of halogen-free flame retardant; 0.5-5 parts of flame retardant synergist; 2-8 parts of plasticizer; 0.2-0.5 parts of chain extender; 0.2-1 parts of an antioxidant; 0.3-0.8 parts of lubricant. The preparation method comprises the following steps: firstly, powdering a halogen-free flame retardant, a synergistic flame retardant, a chain extender, a lubricant and an antioxidant to form an auxiliary agent package; adding polyamide resin into a high-speed mixer, uniformly adding a plasticizer, adding a flame-retardant silane coupling agent for low-speed mixing, and adding a mixing auxiliary agent package for high-speed mixing to obtain a mixed material; the materials are added into a double-screw extruder through a main feeding port, and glass fibers are added through side feeding, and the composite material with excellent comprehensive performance is prepared through extrusion granulation.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a flame-retardant coupling agent synergistic glass fiber reinforced halogen-free flame-retardant polyamide composite material and a preparation method thereof.
Background
The polyamide (PA, commonly called nylon) has good comprehensive properties including mechanical properties, heat resistance, abrasion resistance, chemical resistance and self-lubricating property, has low friction coefficient, has certain flame retardance, is easy to process, is very suitable for reinforcing and modifying glass fibers and other fillers, improves the performance and expands the application range. As an engineering plastic, the polyamide is widely applied to the fields of automobiles, household appliances, electronic appliances, electric tools, aerospace and the like. At present, the environmental protection problem and the energy source problem are important attention directions of the country, the new energy source field becomes a research hot spot, and in recent years, the automobile industry emerges a plurality of new energy source automobile brands with competitive power batteries, charging piles, electronic appliances and other fields matched with the automobile brands have brought forth good development opportunities. With the gradual increase of the market demand for the performance of the product, in the electronic and electric industry, higher requirements are put on the strength, environmental protection performance, flame retardant performance, electric performance, dimensional stability and the like of the product. In particular, IEC (international electrotechnical association of the european union) proposes in IEC60695 standards for household and similar electrical appliances that the flame retardant properties of plastic parts used for long-term unattended appliances must be: the glowing filament contact material ignition temperature (GWIT) of UL94V 0 and 750 ℃ is not all the way up, and GWIT temperature 850 ℃ and Comparative Tracking Index (CTI) 600V are also required for certain components such as connectors, cable plugs, etc. in some more demanding applications.
Glass fiber is an inorganic nonmetallic material with excellent performance, and has the advantages of good insulativity, strong heat resistance, good corrosion resistance and high mechanical strength, but has the disadvantages of brittle property and poor wear resistance. The yarn is manufactured by taking six ores of pyrophyllite, quartz sand, limestone, dolomite, loam and boron-magnesium stone as raw materials through the processes of high-temperature melting, wire drawing, winding, weaving and the like, the diameter of a monofilament is several micrometers to twenty-several micrometers, which is equivalent to 1/20-1/5 of that of a hair, and each bundle of fiber precursor consists of hundreds or even thousands of monofilaments. Glass fibers are commonly used as reinforcing materials in composite materials, electrical and thermal insulation materials, circuit substrates, and the like in various areas of national economy. The existing glass fiber material has good alkali resistance, but poor acid resistance and water resistance, and the flame retardant property of the glass fiber needs to be further improved.
At present, a brominated flame-retardant system is widely applied to flame retardant modification of a polyamide material due to high flame retardant efficiency, excellent processability and small influence on material performance, but the brominated flame-retardant polyamide material is generally low in glow wire and tracking resistance effect, generally, GWIT can only reach 750 ℃, CTI can only reach 250V, and many electronic and electric appliance application occasions cannot be met. According to the traditional improvement method, a flame retardant such as melamine flame retardant which is generally and conventionally used is continuously added to the conventional brominated flame-retardant reinforced polyamide material, and although the glow wire temperature of the polyamide material can be increased to improve the flame retardant performance of the polyamide material, the mechanical properties of the material are very poor, especially for the brominated flame-retardant reinforced PA66 material, the melamine flame retardant is decomposed due to high processing temperature, so that the composition has the conditions of poor rigidity, low impact strength, insufficient toughness and the like, and the composition can not be normally extruded and granulated and subjected to subsequent injection molding under more serious conditions, and finally the composition has no practical application value.
The nylon 66 halogen-free flame-retardant glass fiber reinforced thermoplastic engineering plastic has the advantages of light specific gravity, good thermal stability, good mechanical property, excellent electrical property, good flame retardant property and the like, and the smoke density generated after combustion is small, the toxicity is low, the cost is low, the environment-friendly requirement is met, but the tensile strength of the corresponding material is low, and the corresponding material cannot be used in specific fields, such as fields requiring ultra-high tensile property; the impact strength of the material is low, corresponding toughening modification is needed, and the modification has a certain influence on the flowability of the material.
Therefore, how to provide a halogen-free flame-retardant reinforced nylon 66 material with excellent comprehensive performance to solve the defects existing in the prior art is the subject to be studied and solved by the invention.
Disclosure of Invention
The invention aims to provide a flame-retardant coupling agent synergistic glass fiber reinforced halogen-free flame-retardant polyamide composite material and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the flame-retardant coupling agent synergistic glass fiber reinforced halogen-free flame-retardant polyamide composite material comprises the following raw materials in parts by weight:
according to a further technical scheme, the polyamide is polyamide with carbon chains having carbon atoms less than or equal to 6 carbon atoms and is selected from at least one of PA66, PA6 and PA56, and the relative viscosity of the polyamide resin is 2-2.8.
According to a further technical scheme, the flame-retardant silane coupling agent is a self-made halogen-free silane coupling agent, and the preparation process is as follows:
taking 10 g of ammonium polyphosphate (APP), and dissolving the ammonium polyphosphate (APP) with the polymerization degree n=100-500 in deionized water; adding 500ml of ethylene glycol as a reaction medium, dropwise adding 3-aminopropyl triethoxysilane (APTES) according to a reaction molar ratio, and stirring at 90 ℃ for reaction for 5-8 hours; and after the reaction is finished, carrying out suction filtration, and washing the obtained product with absolute ethyl alcohol for a plurality of times to obtain the flame-retardant silane coupling agent.
According to a further technical scheme, the glass fibers are alkali-free glass fibers. Comprises common glass fiber and flat glass fiber with the flatness ratio of 2-5.
According to a further technical scheme, the halogen-free flame retardant is prepared by compounding organic aluminum hypophosphite, melamine polyphosphate (MPP) and anhydrous zinc borate according to a mass ratio of 6:1:1-6:2:2;
the organic aluminum phosphinate is one or more of diethyl aluminum phosphinate, dipropyl aluminum phosphinate, phenyl aluminum phosphinate, methyl ethyl aluminum phosphinate, methyl phenyl aluminum phosphinate and carboxyethyl aluminum phosphinate.
According to a further technical scheme, the flame retardant synergist is one or more of nano montmorillonite, boehmite and kaolin.
Further technical scheme, the plasticizer is one or more of N-butyl benzene ring amide, O/p-toluene sulfonamide (O/PTSA), N-ethyl p-toluene sulfonamide (NEPTSA) and N-ethyl O/p-toluene sulfonamide (NEOPTSA).
According to a further technical scheme, the chain extender is a compound of bisoxazoline, biscaprolactam, bisoxy, dicyclo carboxylic anhydride and bisenoxide groups.
According to a further technical scheme, the antioxidant is one or more of amine, phenol and phosphite antioxidants.
According to a further technical scheme, the lubricant is one or more of calcium stearate, silicone powder, pentaerythritol stearate, ethylene bis-stearamide and OP wax.
Further, the preparation method of the flame-retardant coupling agent synergistic glass fiber reinforced halogen-free flame-retardant polyamide composite material comprises the following steps:
firstly, powdering a halogen-free flame retardant, a synergistic flame retardant, a chain extender, a lubricant and an antioxidant through a powdering machine to form a uniformly mixed auxiliary agent package, wherein the auxiliary agents subjected to powdering can be fully mixed, and the functions of micro auxiliary agents can be better exerted;
adding polyamide resin into a high-speed mixer, uniformly adding a liquid plasticizer, adding a self-made flame-retardant silane coupling agent, mixing for 0.5-1.5 min at a low speed of 250-350 rpm, adding a mixing auxiliary agent bag into the high-speed mixer, mixing for 1.5-3 min at a high speed of 500-600 rpm, and finally obtaining a uniformly mixed material;
if the plasticizer is solid, mixing the plasticizer with other solids, powdering to prepare the auxiliary agent packet, and then adding the auxiliary agent packet and the polyamide resin into a high-speed mixer to be mixed at a high speed of 500-600 rpm for 1.5-3 min;
step two, adding the uniformly mixed materials obtained in the step one into a double-screw extruder through a main feeding port, and adding glass fibers through side feeding; the extrusion temperature of the double screw extruder is 230-270 ℃, and the flame-retardant coupling agent synergistic glass fiber reinforced halogen-free flame-retardant polyamide composite material is prepared by extrusion granulation.
The working principle and the advantages of the invention are as follows:
aiming at the defects of poor 'lampwick effect' and self flame retardant property of glass fiber and obvious mechanical property reduction of the material caused by large addition amount of halogen-free flame retardant in the polyamide halogen-free flame retardant glass fiber reinforced material, the invention particularly develops a modification scheme for carrying out synergistic flame retardance by using flame retardant modified glass fiber as a reinforcing agent and matching with a special halogen-free flame retardant system, thereby obtaining the halogen-free flame retardant reinforced polyamide material with excellent comprehensive property.
By adding the flame-retardant silane coupling agent, an acid source and an air source are added, a synergistic flame-retardant effect is formed with the aluminum alkyl hypophosphite, the flame-retardant effect of the composite material is better, and the addition amount of the aluminum alkyl hypophosphite is reduced from 18% to 13%, so that the same flame-retardant effect can be achieved. The introduced silane coupling agent ensures that the binding force between the components of the composite material is better, and the combination of the silane coupling agent and the components ensures that the composite material maintains higher mechanical property. The flame retardant property and CTI of the flame retardant reinforced polyamide material prepared by the invention can reach 1.6mmVO grade and 600V, the mechanical property is obviously superior to that of the common halogen-free flame retardant reinforced polyamide material, and the novel requirements of the application field of electronic appliances can be widely met.
According to the invention, the reactive cross-linking agent is introduced into the halogen-free phosphinate flame-retardant reinforced nylon system, so that the halogen-free phosphinate flame-retardant reinforced nylon system can be subjected to partial cross-linking reaction in the extrusion and injection molding processes, and a micro-network structure is formed in a nylon matrix, so that the partial performance of the traditional thermoplastic material is improved. The micro-network structure does not influence the recoverability of the material, can improve the flame retardant property and mechanical strength of the material, and more importantly, can improve the strength and density of a carbon layer formed by the material in the process of burning, so that the heat insulation capability is greatly improved. Compared with the cross-linking reaction of the existing material in the combustion process, the micro-cross-linking reaction in the extrusion and injection molding processes can directly improve the carbon forming performance of the material, and has the advantages of higher speed, higher strength of a carbon layer and better barrier property. The material of the invention has small preparation difficulty and obvious effect.
Advantages of the present invention over the prior art include:
1. by adding 3-aminopropyl triethoxysilane for ammonium polyphosphate (APP) modification, the two are combined together through cation exchange reaction, and APP is introduced to have the functions of an acid source and an air source; meanwhile, a large amount of-Si-OH existing in the silane coupling agent molecules is introduced, so that the heat stability of APP is improved, the compatibility of the flame retardant and a polyamide matrix is improved, and meanwhile, the compatibility of glass fibers and polyamide resin is improved.
2. The enhanced fiber is synergistically modified by the ammonium polyphosphate modified silane coupling agent, so that the interfacial compatibility of the fiber and the polymer material is improved, the mechanical property of the fiber enhanced polymer composite material is improved, and a certain flame retardant property is essentially given to the fiber. In the combustion process of the composite material, the modified silane coupling agent catalyzes polymer carbonization on the fiber surface, promotes fiber surface roughening, cuts off a transmission channel of combustible molecules, and further inhibits the candlewick effect of the glass fiber.
3. By using ammonium polyphosphate as a common 'acid source' in the intumescent flame retardant, the ammonium polyphosphate can promote the polymer material to form carbon, and an intumescent carbon layer is formed to play a role in isolating combustible gas and finally interrupting combustion. The aluminum alkyl phosphinate flame retardant has the structure that the P-C bond replaces the traditional P-O-C bond, so that the heat stability and the water resistance of the flame retardant are improved, the aluminum alkyl phosphinate and ammonium polyphosphate modified silane coupling agent are used for synergetically flame retarding through a gas phase and a condensation camera, on one hand, the aluminum alkyl phosphinate flame retardant is decomposed into non-volatile aluminum phosphate and promotes carbonization of polyamide resin, and the formed expansion layer can play a role in shielding heat, air and decomposition products to play a role in flame retarding, on the other hand, the aluminum alkyl phosphinate flame retardant is decomposed into volatile phosphorus compounds, flame retardance is generated through inhibiting flame, carbonization of the polyamide resin is improved, the residual rate of phosphorus and aluminum is improved, and thus the barrier effect in a condensation phase is improved.
4. APP is easy to absorb moisture, and the APP is easy to cause material degradation when added into polyamide. The polyamide material contains a large amount of highly polar amide groups in its molecular chain, and the presence of small amounts of moisture and impurities during high temperature treatment may cause hydrolysis thereof, so that the addition of flame retardants may cause a decrease in the molecular weight and mechanical properties of the composite. The polyamide resin is a hybrid chain polymer, amino and carboxyl groups with reactivity are generated at the tail end of a molecular chain after the material is degraded in water, and a chain extender containing two or more reactive functional groups is added in the processing process to carry out coupling or branching reaction with active groups generated by degradation, so that the molecular weight and viscosity of the material can be improved, and the reduction of the material performance caused by degradation is compensated.
Drawings
FIG. 1 is a synthetic reaction scheme of a flame retardant silane coupling agent according to an embodiment of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings and examples:
examples: the present invention will be described in detail with reference to the drawings, wherein modifications and variations are possible in light of the teachings of the present invention, without departing from the spirit and scope of the present invention, as will be apparent to those of skill in the art upon understanding the embodiments of the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the terms "comprising," "including," "having," and the like are intended to be open-ended terms, meaning including, but not limited to.
The term (terms) as used herein generally has the ordinary meaning of each term as used in this field, in this disclosure, and in the special context, unless otherwise noted. Certain terms used to describe the present disclosure are discussed below, or elsewhere in this specification, to provide additional guidance to those skilled in the art in connection with the description herein.
Flame-retardant coupling agent synergistic glass fiber reinforced halogen-free flame-retardant polyamide composite material and preparation method thereof
The present invention will be further described with reference to examples 1 to 14 and comparative examples 1 to 3. The raw materials are weighed according to the proportions shown in Table 2 and Table 4, mixed in a high-speed mixer, and extruded and granulated into the composite material by a double screw. The composite material prepared in each example was injection molded into the desired test bars and then performance tested. FIG. 1 is a synthetic reaction scheme of a flame retardant silane coupling agent.
The performance tests in the comparative examples and examples of the present invention were performed according to the following criteria:
tensile strength testing was performed according to GB/T1040.2-2006 standards;
flexural strength was carried out according to GB/T9341-2008 standard;
impact strength was carried out according to GB/T1043.1-2008 standard;
flame retardant property test according to UL94 standard requirement, injection molding size is (125 mm×13mm×1.6 mm) standard combustion sample bar, test is carried out according to UL94 standard, flame is applied for 10s for the first time, after flame time t1 is recorded, flame is applied for 10s for the second time, and after flame time t2 and after flame time t3 are recorded. The combustion grade criteria are shown in Table 1.
The CTI value of the sample was determined according to GB/T4207-2003 method for determining the comparative tracking index and tracking resistance index of solid insulation under humid conditions. The solid electrical insulation was tested for its relative resistance to tracking when exposed to water containing impurities under the action of an electric field.
Table 2 evaluation results of test Performance of Polyamide composite materials according to the proportions of examples 1 to 8
TABLE 3 Material Performance test results
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 |
| Tensile Strength | 165 | 160 | 120 | 150 | 160 | 170 | 162 | 156 |
| Flexural Strength | 250 | 246 | 195 | 236 | 244 | 254 | 247 | 240 |
| Notched impact Strength | 10.5 | 10 | 11 | 10.1 | 10.3 | 11.2 | 10.3 | 10.3 |
| CTI,V | 600 | 600 | 600 | 600 | 600 | 600 | 600 | 600 |
| UL94，1.6mm | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
The styrene-glycidyl methacrylate used as the chain extender in Table 2 was an epoxy chain extender. The antioxidant is a mixture of antioxidant 1098 (hindered phenols) and antioxidant 168 (phosphites), and the mass ratio of the antioxidant to the antioxidant is 1:2.
from examples 1 to 3, it is understood that the method of the present invention can improve the mechanical strength of the short carbon chain polyamide resin, the CTI reaches 600V, and the flame retardant property can reach 1.6mm V0.
As can be seen from examples 1 and 4-8, when the content of the flame retardant silane coupling agent (self-made halogen-free silane coupling agent) in the system is increased and the addition amount of the halogen-free flame retardant diethyl aluminum hypophosphite is reduced, the mechanical properties of the flame retardant reinforced polyamide composite material are continuously improved and the tensile strength reaches 170MPa under the condition that the flame retardant property and CTI value of the system are maintained, so that the flame retardant reinforced polyamide composite material has better application value. Compared with the embodiment of the invention, the flame retardant performance of the material system can not reach 1.6mm V0 level under the condition of adding the higher compound halogen-free flame retardant because the flame retardant silane coupling agent is not added in the comparative examples 1 and 2, and the mechanical properties of the material are greatly influenced.
Table 4 evaluation results of test Performance of the Polyamide composite materials of examples 9 to 14 and comparative examples 1 to 3
TABLE 5 Material Performance test results
The styrene-glycidyl methacrylate used as the chain extender in Table 4 was an epoxy chain extender. The antioxidant is a mixture of antioxidant 1098 (hindered phenols) and antioxidant 168 (phosphites), and the mass ratio of the antioxidant to the antioxidant is 1:2.
as can be seen from examples 9-11 and comparative example 3, the addition of the flame retardant synergist nano montmorillonite, boehmite and kaolin has obvious flame retardant synergistic effect, and the material can realize V0 flame retardance under the condition of lower halogen-free flame retardant addition. As is clear from examples 12 to 14 and comparative example 4, the mechanical properties of the materials added with the plasticizer are higher than 2 parts, which has a great relationship with the plasticizer that can well reduce the melting point of the polyamide plastic and further improve the fluidity and processability of the polyamide plastic, so that the composite material system can be better dispersed and compatible.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (11)
1. A flame-retardant coupling agent synergistic glass fiber reinforced halogen-free flame-retardant polyamide composite material is characterized in that: the raw materials comprise the following components in parts by weight:
30-50 parts of polyamide resin;
0.3-4 parts of flame-retardant silane coupling agent;
20-60 parts of glass fiber;
10-18 parts of halogen-free flame retardant;
0.5-5 parts of flame retardant synergist;
2-8 parts of plasticizer;
0.2-0.5 parts of chain extender;
0.2-1 parts of an antioxidant;
0.3-0.8 parts of lubricant.
2. The flame retardant coupling agent synergistic glass fiber reinforced halogen-free flame retardant polyamide composite material according to claim 1, characterized in that: the polyamide is polyamide with carbon chains having carbon atoms less than or equal to 6 carbon atoms and is selected from at least one of PA66, PA6 and PA56, and the relative viscosity of the polyamide resin is 2-2.8.
3. The flame retardant coupling agent synergistic glass fiber reinforced halogen-free flame retardant polyamide composite material according to claim 1, characterized in that: the flame-retardant silane coupling agent is a self-made halogen-free silane coupling agent, and the preparation process is as follows:
dissolving 10 g of ammonium polyphosphate in deionized water; adding 500ml of ethylene glycol as a reaction medium, dropwise adding 3-aminopropyl triethoxysilane according to a reaction molar ratio, and stirring at 90 ℃ for reaction for 5-8 hours; and after the reaction is finished, carrying out suction filtration, and washing the obtained product with absolute ethyl alcohol for a plurality of times to obtain the flame-retardant silane coupling agent.
4. The flame retardant coupling agent synergistic glass fiber reinforced halogen-free flame retardant polyamide composite material according to claim 1, characterized in that: the glass fiber is alkali-free glass fiber.
5. The flame retardant coupling agent synergistic glass fiber reinforced halogen-free flame retardant polyamide composite material according to claim 1, characterized in that: the halogen-free flame retardant is prepared by compounding organic aluminum hypophosphite, melamine polyphosphate and anhydrous zinc borate according to a mass ratio of 6:1:1-6:2:2;
the organic aluminum phosphinate is one or more of diethyl aluminum phosphinate, dipropyl aluminum phosphinate, phenyl aluminum phosphinate, methyl ethyl aluminum phosphinate, methyl phenyl aluminum phosphinate and carboxyethyl aluminum phosphinate.
6. The flame retardant coupling agent synergistic glass fiber reinforced halogen-free flame retardant polyamide composite material according to claim 1, characterized in that: the flame retardant synergist is one or more of nano montmorillonite, boehmite and kaolin.
7. The flame retardant coupling agent synergistic glass fiber reinforced halogen-free flame retardant polyamide composite material according to claim 1, characterized in that: the plasticizer is one or more of N-butyl benzene ring amide, o/p-toluene sulfonamide, N-ethyl p-toluene sulfonamide and N-ethyl o/p-toluene sulfonamide.
8. The flame retardant coupling agent synergistic glass fiber reinforced halogen-free flame retardant polyamide composite material according to claim 1, characterized in that: the chain extender is a compound of bisoxazoline, biscaprolactam, bisoxy, dicyclo carboxylic anhydride and bisenoxide groups.
9. The flame retardant coupling agent synergistic glass fiber reinforced halogen-free flame retardant polyamide composite material according to claim 1, characterized in that: the antioxidant is one or more of amine, phenol and phosphite antioxidants.
10. The flame retardant coupling agent synergistic glass fiber reinforced halogen-free flame retardant polyamide composite material according to claim 1, characterized in that: the lubricant is one or more of calcium stearate, silicone powder, pentaerythritol stearate, ethylene bis-stearamide and OP wax.
11. A method for preparing a flame-retardant coupling agent synergistic glass fiber reinforced halogen-free flame-retardant polyamide composite material, which is used for preparing the flame-retardant coupling agent synergistic glass fiber reinforced halogen-free flame-retardant polyamide composite material according to any one of claims 1-10, and is characterized in that: the preparation method comprises the following steps:
firstly, powdering a halogen-free flame retardant, a synergistic flame retardant, a chain extender, a lubricant and an antioxidant through a powdering machine to form a uniformly mixed auxiliary agent bag;
adding polyamide resin into a high-speed mixer, uniformly adding a plasticizer, adding a flame-retardant silane coupling agent, mixing at a low speed of 250-350 rpm for 0.5-1.5 min, adding a mixing auxiliary agent package into the high-speed mixer, mixing at a high speed of 500-600 rpm for 1.5-3 min, and finally obtaining a uniformly mixed material;
if the plasticizer is solid, mixing the plasticizer with other solids, powdering to prepare an auxiliary agent packet, and then adding the auxiliary agent packet and the polyamide resin into a high-speed mixer to be mixed at a high speed of 500-600 rpm for 1.5-3 min;
step two, adding the uniformly mixed materials obtained in the step one into a double-screw extruder through a main feeding port, and adding glass fibers through side feeding; the extrusion temperature of the double-screw extruder is 230-270 ℃, and the flame-retardant coupling agent synergistic glass fiber reinforced halogen-free flame-retardant polyamide composite material is prepared by extrusion granulation.
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